Production of pseudo-kryptogenins from kryptogenins



Patented oeeze, 1950 2,535,073

UNITED STATES PATENT OFFICE PRODUCTION OF PSEUDO-KRYPTOGENINS FROM KRYPTOGENINS Stephen Kaufmann and George Rosenkranz, Mexico City, Mexico, assignors to Syntex, S. A., Mexico City, Mexico, a corporation of Mexico No Drawing. Application September 19, 1949, I Serial No. 110,623

4Claims.' (c1. zed-239.55) 2. '1'

The present invention relates to anovelprocess The foregoing reaction has been found to be for the production of cyclopentanophenanthrene substantially complete in a relatively short length compounds. More particularly the present inof time as, for example, about one hour and the vention relates to the production of valuable horyields were substantially better than the reaction mone intermediates such as pseudo-kryptogenin 5 at temperatures of the order of 200 C. diacetate and pseudo-5,6 dihydrokryptogenin di- The following specific examples serve to illusacetate from kryptogenin diacetate and 5,6 ditrate but are not intended to limit the present hydrokryptogenin diacetate. invention:

Marker et al. (J. A. C. S. 69, 2, 200, 1947) re- Example I ported the production of pseudo-kryptogenin from kryptogenin diacetate by heating the di- 10 grams of kryptogenin diacetate were disacetate with acetic anhydride at 200 C. for twelve solved in 30 cc. of acetic anhydride and thereafter hours. Similarly, in U. S. Patent No. 2,352,852 100 milligrams of toluene sulphonic acid were granted July 4, 1944, Marker discloses the proadded. The mixture was refluxed for one hour duction of various pseudo derivatives by the relaand then poured into a water and ice mixture. tively high temperature prolonged heating of the The resulting precipitate was filtered off and recorresponding steroidal sapogenin. crystallized from'methanol. A yield of 8 grams The surprising discovery has been made, howof p u ry e diacetate h vin a m l ing ever, in accordance with the present invention point of 9394 C. were obtained. that in the special instance of the diacetates of kryptogenin and 5,6 dihydrokryptogenin, the cor- Example H e ponding pseudoyp diacetate and 10 grams of 5,6-dihydrokrytogenin were disp -M d yd yp n n dia t t ay be solved in cc. of acetic anhydride and thereafter obtained in excellent yield by reac With milligrams of toluene sulphonic acid were tic a y d a ux ra u s; i. i 25 added. The mixture was refluxed for one hour the neighborhood of 140 C. and in the presence and poured into a water and ice mixture. The

of a catalytic amount of an aromatic sulphonic resultant precipitate was filtered off and recrysacid such as toluene sulphonic acid. tallized from methanol. A yield of 8 grams of The mechanism of the reaction can be reprepseudo-5,6 dihydrokryptogenin diacetate having sented by the following equation: an a melting point of 9698 C. were obtained.

om on. CH3 on, OHzOAc OH; on, CHflOAO c oHioHioH Acetic anhydride tho-creamer! and catalyst I OH; H OH: o 0. OH

Kryptogenln diaoetate CH: CH:

CHQOAO OHeCHn JH Pseudo ln'yptogenin diacetete and pseudo-5,6 dihydrokryptogenin comprising reacting a compound selected from the group consisting ofkryptogenin diacetate and: 5,6 dihydrokryptogenin diacetate, with acetic It will be obvious to those skilled in the art that various changes may be made without departing from the spirit of the invention and therefore the invention is not limited to what is described in the specification but only as indicated in the appended. claims.

We claim:

1. A process for the production of a cyclopentanophenanthrene compound selected from the group consisting of pseudo-kryptogenin diacetate.

and pseudo-5,6 dihydrokryptogenin diaeetate comprising reacting a compound selected from the group consisting of kryptogenin diacetate and 5,6 dihydrokryptogenin diacetate, with acetic anhydride under reflux conditions in the presence of a catalytic amount of an aromatic. sulphonic acid.

2. A process for the production of a cyclopentanophenanthrene compound selected from thegroup consisting of pseudo-kryptogenin diacetate diacetate anhydrideunder reflux conditions inthe presence of a catalytic amount. of toluene sulphonic acid.

3. A process for the production of pseudokryptogenin diacetate comprising reacting kryptogenin diacetate with acetic anhydride under reflux conditions in the presence of a catalytic amount of toluene sulphonic acid.

4., A. process for the production of pseudo-5,6 dihydrokryptogenin diacetate comprising reacting 5,6 dihydrokryptogenin diacetate with acetic anhydride under reflux conditions in the presence of a catalytic amount of toluene sulphonic acid.

STEPHEN KAUFMANN. GEORGE ROSENKRANZ.

REFERENCES CITED The folIowing references are of record in the fileof this patent:

UNITED STATES PATENTS Number Name Date 2,352,852 Marker July 4, 1944 2,468,832; Wagnero Oct. 81. 9 6

FOREIGN PATENTS Number Country Date 235,924 Switzerland Mar. 1, 1945 

1. A PROCESS FOR THE PRODUCTION OF A CYCLOPENTANOPHENANTHRENE COMPOUND SELECTED FROM THE GROUP CONSISTING OF PSEUDO-KRYPTOGENIN DIACETATE AND PSEUDO-5,6 DIHYDROKRYPTOGENIN DIACETATE COMPRISING REACTING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF KRYPTOGENIN DIACETATE AND 5,6 DIHYDROKRYPTOGENIN DIACETATE, WITH ACETIC ANHYDRIDE UNDER REFLUX CONDITIONS IN THE PRESENCE OF A CATALYTIC AMOUNT OF AN AROMATIC SULPHONIC ACID. 